Low-Valent Iron Mono-Diazadiene Compounds: Electronic Structure and Catalytic Application

被引：44

作者：

Lichtenberg, Crispin ^{[1
]}

Adelhardt, Mario ^{[2
]}

Gianetti, Thomas L. ^{[1
]}

Meyer, Karsten ^{[2
]}

de Bruin, Bas ^{[3
]}

Gruetzmacher, Hansjoerg ^{[1
]}

机构：

[1] ETH, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland

[2] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany

[3] Univ Amsterdam, Fac Sci, Dept Homogeneous Catalysis, vant Hoff Inst Mol Sci, NL-1090 GS Amsterdam, Netherlands

来源：

ACS CATALYSIS | 2015年 / 5卷 / 10期

基金：

瑞士国家科学基金会;

关键词：

iron diazadiene compounds; electronic structure determination; methylamine-borane; dehydrogenative polymerization; homogeneous catalysis; AMINE-BORANE ADDUCTS; AMMONIA-BORANE; SPIN-STATE; ALPHA-DIIMINE; BASIS-SETS; COMPLEXES; DEHYDROGENATION; LIGANDS; INNOCENT; ROUTE;

D O I：

10.1021/acscatal.5b01416

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A series of monodiazadiene diolefin iron compounds, [Fe(trop(2)dad)(L)] (4; L = neutral ligand), has been prepared by one-electron oxidation of the Fe-I species [NaFe-(trop(2)dad)(thf)(3)] (dad = diazadiene; trop = 5H-dibenzo[a,d]-cyclohepten-5-yl). The electronic structures of compounds 4 were investigated by NMR and Mossbauer spectroscopy, single-crystal X-ray diffraction, solid- and liquid-phase magnetic susceptibility measurements, and DFT calculations. Compounds of type 4 with labile ligands L were found to be active (pre)catalysts for the dehydrogenative coupling of (alkyl)amine-boranes. Remarkably high activities were observed, especially for the homogeneous dehydrogenative polymerization of methylamine-borane.

引用

页码：6230 / 6240

页数：11

共 73 条

[1] SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].

ADDISON, AW ;

RAO, TN ;

REEDIJK, J ;

VANRIJN, J ;

VERSCHOOR, GC .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07) :1349-1356

[2]

Ahlrichs R., TURBOMOLE VERSION 6

[3]

Alcaraz G., 2010, ANGEW CHEM, V122, P7326

[4] Coordination and Dehydrogenation of Amine-Boranes at Metal Centers [J].

Alcaraz, Gilles ;

Sabo-Etienne, Sylviane .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (40) :7170-7179

[5]

[Anonymous], 2001, PQS VERSION 2 4

[6] AN ALGORITHM FOR THE LOCATION OF TRANSITION-STATES [J].

BAKER, J .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1986, 7 (04) :385-395

[7] Iron Complex-Catalyzed Ammonia-Borane Dehydrogenation. A Potential Route toward B-N-Containing Polymer Motifs Using Earth-Abundant Metal Catalysts [J].

Baker, R. Tom ;

Gordon, John C. ;

Hamilton, Charles W. ;

Henson, Neil J. ;

Lin, Po-Heng ;

Maguire, Steven ;

Murugesu, Muralee ;

Scott, Brian L. ;

Smythe, Nathan C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (12) :5598-5609

[8] Synthesis, reactivity, and solid state structures of four-coordinate iron(II) and manganese(II) alkyl complexes [J].

Bart, SC ;

Hawrelak, EJ ;

Schmisseur, AK ;

Lobkovsky, E ;

Chirik, PJ .

ORGANOMETALLICS, 2004, 23 (02) :237-246

[9] Low-valent α-diimine iron complexes for catalytic olefin hydrogenation [J].

Bart, SC ;

Hawrelak, EJ ;

Lobkovsky, E ;

Chirik, PJ .

ORGANOMETALLICS, 2005, 24 (23) :5518-5527

[10] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

← 1 2 3 4 5 6 7 8 →